Sulphonated terpene product and method of producing same



Patented June 4, 1935 SULPHONAT-ED TERPENE PROD' UCT METHOD OF PRODUCING SAME Alfred L. Bummelsburg Wilmington, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 28, 1932, Serial No. 614,281

z 2 Claims.

This invention relates to sulphonated terpene products and methods for their production, and more particularly to products formed by the sulphonation of mixtures of a polymerized terpene 5 mixture, known as dipolymer, and a higher fa ty acid or ester thereof, or aliphatic, aro-alipha ic, or aromatic compounds containing active groups such as COOH, COC1, -C=O, CH=0, --Cl,'OH, -NH:, -CONH2, O=C0-C=O, or aromatic hydrocarbons, or their substitution products.

In accordance with the present invention, it is found possible to sulphonate mixtures containing fatty acids or their esters such as castor oil, ricinoleic a'cid, olein, oleic acid, olive oil, linseed oil, corn oil, stearic acid, palmitic acid, a resin acid such as abietic acid, etc., together with polymerized tempene mixtures, such as light or dark dipolymer, or mixtures such as light or dark dipolymer with compounds such as butyl alcohol, laurol, abietyl alcohol, stearol, amyl chlorides, benzyl chloride, naphthols, phenols, cresols, naphthylamines, aniline, acid amides, acid chlorides, phthalic anhydride, acetic anhydride, toluene, benzene or naphthalene,'or mixtures of dipolymer, fatty acids, and any of the above mentioned substances, using as a. condensing and sulphonating agent chlorosulphonic acid, acetyl sulphuric acid, or fuming or concentrated sulphuric acid. Dipolymer, as the term is herein employed, is a product consisting of polymerized terpene hydrocarbons and is produced by the polymerization of dipentene, turpentine or pine oil, by various methods, for example, those outlined in the patents to Irvin W. Humphrey, 1,691,065, 1,691,067, 1,691,068, and 1,691,069 dated November 13 1928. The term is herein used to broadly designate substances of this type. Ac-

cording to its method of production the dipolymer is known as light or dark dipolymer.

As pointed out in the application of Runmielsburg and Little, Serial No. 558,832, filed August 22, 1931, it is found that dipolyme'r, or similar poly-v merized terpene mixtures, may be converted to water soluble products upon treatment with concentrated or fuming sulphuric acid, or chlorosulphonic acid, the product being capable of forming metallic salts.

As pointed out in the above application, both the product known as sul-' phonated dipolymer and its alkali salts are found to be very effective as wetting-out agents; that is,

when added to water or various aqueous solutions they enable fibers, powders, or other substances, to be wetted more readily than would otherwise be the case.

For example, they promote the speed and efllciency with which wool may be wetted and they also make possible the pasting of dye stufis, powders, etc., which are sometimes very diflicult to paste with water alone. These-products are also effective emul- 5 sifying and dispersing agents,

It is also known that the various fatty esters and acids mentioned above, can be. sulphonated and used as wetting out agents. Y.

However, when the fat, fatty acid or other substances and polymerized terpenes are mixed together prior to sulphonation a different product is obtained from that made by mixing the sulphonated products after sulphonation of the two components separately, the unsaturated nature of the polymerized terpenes lending toward their case of condensation with fats or substituted aliphatic, aromatic or araliphatic hydrocarbons, or the aromatic hydrocarbons themselves, a reaction similar to the Friedel and Crafts reaction probably occurring in the case of aromatic anhydrides, or araliphatic halides in the presence of the sulphonating acid. Specifically the new products thus obtained are easier to make than sulphonated dipolymer, are more soluble in water and are more resistant to decomposition by acids.- Both the free sulphonated acid products and their salts obtained by theirneutralization are good v emulsifying agents for pine oil, terpineol, hexalin, tetralin, stearol, etc. and other oils used in the textile industry and are very stable to acids such as sulphuric, hydrochloric and acetic acids and to salts such as magnesium chloride and common salt in concentrations up to 5%. Either the acid or its sodium salt is miscible with pine oil or terpineol in any proportion. For some purposes it is preferable to use the product in pine oil solution.

For example, a product obtained by treating a suitable mixture of oleic acid and polymerized 40 terpenes with chlorosulphonic acid is more easily handled than a product obtained by sulphonating either oleic acid or dipolymer and, in addition, the vigorous nature of this reaction is greatly lowered because of a simultaneous condensation 45 reaction which apparently occurs along with sulphonation. The products obtained will in general dissolve in water to give clear soapy solutions before being neutralized.

The product obtained when using oleic acid and a polymerized terpene mixture known as dark dipolymer is an oil containing about 3.0-6.5% sulphur and having an acid number of -110 and a saponiflcation number of -200, and usually containing some water. The iodine value of the acid terpene mixture before sulpho nation is about 135; after sulphonation about 40. The rhodanometric iodine number of the unsulphonated mixture is about 84; after sulphonation about 20.

. Example No. 1-

As an example of a preparation in accordance with the invention, a mixture of 200 grams of technical oleic acid, acid number 189.2, saponification number 196.7, rhodanometric iodine number 85, and 200 grams of dark dipolymerjwhich is a mixture of terpenes containing varying per- 1 centages of higher polymers, is treated with 300 grams of technical chlorosulphonic acid by adding the latter gradually for three-quarters of an hour to the mixture held at 25-30 C. while stirring vigorously and cooling. After addition of the acid the temperature is raised to 70 C. with continued agitation for several hours until evolution of hydrogen chloride ceases. The mixture is then cooled and 700 cc. of saturated common salt solution is added while cooling and stirring. After standing for two to four days. the lower layer of sodium chloride solution is separated thus washing the oil. One or two additional washes with concentrated sodium chloride solution may be given. The yield of sulphonated oil,'on a dry basis, so obtained amounts to 400 to v600 grams and has the properties indicated above.

The washed oil may be then neutralized with a suitable base or alkaline solution, for example, pyridine, triethanolamine, or a 30% caustic soda solution, although solutions of sodium or potassium carbonate or ammonia may be used. This neutralizing agent is dropped in slowly with stirring and, usually cooling until the oil becomes neutral. After such treatment, the oil contains 10 to 40% of water.

In the practice of the above process the proportions and quantities of substances used may vary widely as may the conditions under which the reaction takes place. For example, the ratio of fatty acid to polymerized terpene mixture may vary from 5 to 0.5 depending upon the nature of the polymerized mixture used. The quantity of chlorosulphonic acid may vary from 0.2 to 5 As another example of the practice of the invention, there is added slowly to 480 grams of sulphuric acid a mixture of 91 grams of technical oleic acid and 75 grams of a polymerized terpene mixture as before with vigorous stirring and cooling taking about three-quarters of an hour while the temperature is kept-at 20 to 30 C. Then the.temperature is raised to 75 to 100 C. for one hour, or until complete sulphonationtakes place after which the temperature is lowered and water is dropped in slowly .with cooling to form a 40-50% solution of acid.

The viscous sulphonated oil which separates. on, standing is washed with a common salt solution or can be separated while containing a amount of acid impurity and dissolved in 600 cc.

of water, then neutralized with a suitable alkaline solution; Suflicient common salt is then added to form 15% salt solution and the neutral sul- -ations of temperatures may also be used.

Example No. 3

As a further example a mixture consisting of 100 g. dark dipolymer and 100 g. oleic acid is added slowly with cooling and agitation to 500 g. concentrated H:S04(95%). The mixture is agitated at room temperature for 12 hours, after which it is diluted to 50% acid strength, the sulphonatedproductseparated and washed with brine, and

a water soluble oil is obtained having an A. N. of

Example N0. 4

As a further example, a mixture containing 200 g. linseed oil fatty acids (acid number of 197 and iodine number of 182) and 160 g. dark dipolymer is treated with 300 g. of a mixture previously prepared by adding 150 g. concentrated sulphuric acid to 150 g. of acetic anhydride slowly at 15 C. The acetyl sulphuric acid mixture is added to the fatty mixture'slowly at 15 C. with vigorous agitation. Afterward the mixture is agitated for several hours at 15 C. The reaction can be completed if desired by heating to 100 C. for several hours. In this reaction, as in others in accordance with this invention, heating is optional after adding the sulphonating acid. After cooling, the mixture is added to one liter of 10% sodium chloride solution with agitation, and the sulphonated oil allowed to separate; a second wash may be necessary. The oil is allowed to stand over. the salt solution for several days before separating. The resultant product dissolves readily in water to give opalescent and sometimes opaque solutions. When neutralized as in theabove example it dissolves in water at any concentrationto give clear solutions. The unneutralized product has an acid number of about and a saponification number of about 200, with a sulphur content of about 3%.. Linseed oilmay be substituted for the fatty acids.- The suipnur content may be increased or decreased accord ingly as the amount of sulphonating agent is in-. creased or decreased. The temperature during the operation may vary widely as before according to the type of product desired, and the amount of polymerized terpene constituents present.

Example No. 5

As a further example, a mixture containing 100 g. dark dipolymer and 60 g. laurol is slowly treated with g. chlo-rosulphonic acid or other sulphonating acid as fuming sulphuric at a temperature of 20-30 C. with vigorous agitation and cooling. After an hour when the acid is added, the temperature is raised to 60-100 C. for several hours with continued agitation. It is then cooled, and washed with 500 cc. 15% salt solution giving about 200 g. product. The washed product is water soluble and possesses powerful emulsifying, dispersing and wetting properties, both before and after neutralization. An alcohol of lower molecular weight than laurol can be used although the desired effectv is somewhat proportional to the length of the alcohol carbon chain.

Example No. 6

In a further example a mixture containing g. light dipolymer and g. benzyl chloride is dropped into 450 g. 101% H2804 during half an hour with agitation and cooling at 25-35" C. The condensation reaction proceeds with vigorous evolution of hydrogen chloride. Agitation is then continued at 80 C. until sulphonation is substantially complete. The sulphonated product separates on diluting the acid mixture to 40% acid strength. It is redissolved in a. small amount of water, neutrafized, and, salted from solution by adding sodium chloride. The dark brown colored solid has wetting properties. In the above example the benzyl chloride may be added after the polymerized terpene is added to the acid, prior to heating, with equivalent results. Approximately 125 g. of product is obtained.

Example No. 7

In another example 26 g. light dipolymer are mixed with 1'? g. phthalic anhydride and added .slowly to 200 g. 101% H2SO4 with cooling at 25- 35" C. The mixture is then heated at 60l00 C. until sulphonation is substantially complete. After cooling and diluting to 40% acid strength a sulphonated product separates which, after washing and neutralizing, is soluble in water and has wetting properties. About 20 g. of product is obtained.

Example N0. 8

, In still another example 350 g. dark dipolymer are added to 700 g. 101% sulphuric acid during a period of half an hour with cooling and agitation keeping the temperature at 25 C. beta naphthol are then added with agitation followed by g. 105% H2804. The -mixture is agitated at room temperature for four.hours after which the temperature is raised to 70 C. for several hours. It is then cooled and, enough water added with cooling to make a 40-50% acid strength. A viscous product separates which is readily soluble in water. After washing and neutralizing 350-400 g. of a dark brown colored product possessing strong wetting properties toward silk, cotton, and rayon, in water, is obtained. In

. the above example the naphthol may be first mixed with the polymerized terpene and the mixture added to the sulphonating agent with equivalent results. Instead of naphthol, phenol or cresol may be used with good results.

Example No. 9

In a further example a mixture consisting of 100 g. dipolymer and 85 g. aniline is slowly added to 250 g. 101% H2804 with stirring and cooling during half an hour. It is then agitated at room temperature for several hours and at 60-100" C. for several hours. After cooling and diluting to 50% acid strength the sulphonated product separates, and can be washed and neutralized as before. In the above example other aromatic primary or secondary amines such as ethyl aniline, naphthylamine, or acid amides, particularly the fatty acid amides, may be used with satisfactory results. The dipolymer may be added to the acid first, followed by the amine or amide with equivalent results.

Example No. 10

As a further example of the treatment of fatty acid, polymerized terpene and substituted hydrocarbon the following mixture consisting of 100 g. dark dipolymer, 106 g. oleic acid and 60 g. benzyl chloride is treated slowly with g. chlorosulphonic acid at 30 C(with cooling and agitation during one hour. It is then heated to 80-l00 C. for several hours, cooled and washed with brine solution. After neutralizing, about 280 g. of a substance is obtained with satisfactory wetting properties, and increased stability toward Ca and Mg salts. In the above example similar results may be obtained by using benzene, xylene, naphthalene, etc. although longer treatment is necessary.

Example N0. 11

As a further example 100 g. naphthalene are added to 600 g. 104% H2804. The mixture is agitated until complete sulphonation occurs. 300 g. dark dipolymer are then added slowly with agitation allowing the temperature to rise slowly until a temperature of from 60-100" C. is reached.

After adding the polymerized terpene the mixture isagitated at a temperature of about 75 C. for several hours or until complete sulphonation occurs. It is then cooled, diluted to 50% acid strength and the viscous dark colored sulphonated product separated, washed with brine and neutralized giving 250 g. product. The waste acid may be treated with CaCOs, until neutral; filtered, and the filtrate then treated with NazCO: until slightly alkaline. After filtering and evapcrating an additional amount of sodium sulpho compound is obtained. In the above example benzene, xylene, etc. may be substituted for naphthalene. Also, the terpene and aromatic hydrocarbon may be mixed prior to sulphonation.

In all the above examples the effect of elevated temperature is to increase the rate of reaction. The same results may be obtained using room temperatures, however, much longer periods of agitation are required. The proportion of components used may be varied depending upon the nature of the polymerized terpene mix.- ture. In many of the cases chlorosulphonic may be used as well as concentrated or fuming sulphuric acid.

While the specific examples relating to the use of fatty acids pointed out above relate to the treatment of oleic acid, castor oil ard linseed oil fatty acids together with polymeriz =.d terpenes, other higher fatty acids, or their 1 rcerides, or

higher fatty acid esters may be similarly treated,

the products obtained with fatty acids being particularly important. However, while the treatment is similar it may be necessary to vary the temperature, proportions of reactants, sulphonating acid, etc. The products obtained will not always possess the same properties, although they will be of the same general type. In "eneral, the products have the emulsifying and wetting out properties indicated above, the calcium, magnesium and similar salts being sufiiciently soluble in water and the free acid or neutral product is soluble in dilute acids, such as sulphuric, hy-

drochloric, acetic, etc., so that the sulphonated derivatives may be used in acidic solutions or hard water.

In certain cases it is found practical to prepare the alkali salts of the sulphonated derivatives by treating the free sulphonic acids with calcium carbonate, filtering, and then treating the solution with alkali carbonate until it is' slightly alkaline to litmus and again filtering. An alkali salt of a sulphonic derivative may then be obtained by evaporation. Instead of using the mixed polymerized terpenes the pure diterpene or higher polymers may be employed. The dipolymer may be obtained as pointed out above by heat treatment of pinene, dipentene, etc., or with heat treatment in connection with a polymerizing catalyst. such as fullers earth, stanriic chloride, or the like. The dipentene may be obtained by first dehydrating either terpineol or pine on and then polymerizing the terpenes. The dipolymer as obtained for sulphonation. may contain a considerable proportion'of pine oil components.

In the following claims it will be understood that the term "higher fatty acid" refers to those acids the esters of which constitute fats. Inasmuch as in the preparation of the most useful sulphonated derivatives these higher fatty acids, or their esters, may be interchangeably used, except for details of procedure as indicated above, they are set forth inthe-claims as equivalents.

It will be understood that where in the claims appended hereto the term higher fatty acid" is product which includes reacting a mixture of a polymerized terpene and a substituted hydrocarbon which is capable of sulphonation, with a sulphonating acid.

3. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with a sulphonating acid.

4. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with a sulphonating acid, and neutralizing the reaction product.

5. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with a sulphonating acid.

6. The process of preparing a sulphonated roduct which includes reacting a mixture of a polymerized terpene and a higher fatty acid with sulphuric acid.

7. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with concentrated sulphuric acid.

8. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with ,471 sulphuric acid and neutralizing the reaction product.

9. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with chlorosulphonic acid. I

10. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with chlorosulphonic acid, and neutralizing the reaction product. I

ii. The process of preparing a sulphona product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with a sulphonating acid, diluting the reacted mixture with an aqueous sodium chloride solution, and

separating the sulphonated product from the aqueous solution.

12. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a higher fatty acid with a sulphonating acid, diluting the reacted mixture with an aqueous sodium chloride solution, separating the sulphonated product from the aqueous solution, and neutralizing the sulphonated product.

13. The sulphonated product of the sulphonation of a mixture of apolymerized terpene and another organic compound which is capable of sulphonation in conjunction with the polymerized terpene.

14. The sulphonated product of the sulphonation of a mixture of a polymerized terpene and a substituted hydrocarbon which is capable of sulphonation. g

. 15. The suiphonated'product of the sulphonation of a mixture of a polymerized terpene and ahigher fatty acid. g

18. The sulphonated product of the treatment of a mixture of a polymerized terpene and a higher fatty acid with concentrated sulphuric acid.

17. The sulphonated product of the'freatment of a mixture of a polymerized terpene and a higher fatty acid with chlorosulphonic acid.

18. A composition comprising a water soluble salt of the sulphonated product of the sulphonation of a mixture of a polymerized terpene, and a higher fatty-acid.

19. The process of preparing a compound of the character specified which includes reacting a mixture of a polymerized terpene and a substituted hydrocarbon which is capable of sulphonation. with a sulphonating acid. I

20. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene with another organic compound which is capable .of sulphonation in con- Junction with the polymerized terpene, with a sulphonating acid and treating the sulphonated product with an alkali. I a

21. The process of preparing a sulphonated product which includes reacting a mixture of a polymerized terpene and a substituted hydrocarbon which iscapable of sulphonation. with a sulphonating acid and treatingthe sulphonated CERTIFICATE OF CORRECTION.

Patent No. 2,003,471. June 4, 19:55.

ALFRED L. num seuns',

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, first oolumn, line '18, for "tempene" read terpene; and that the said Letters Patent should be read withthis correction therein that the same may conform to the record of the case in the Patent- Office.

Signed and. sealed. this 11th day of Ma A. D. 1957.

Henry Van Arsdale (Seal) 4 Acting Commissioner or Patents 

